2,4-bis(4-aminocyclohexylmethyl)cyclohexylamine

ABSTRACT

The triamine 2,4-bis(aminocyclohexylmethyl)cyclohexylamine is prepared by hydrogenation of 2,4-bis(p-aminobenzyl)aniline. The hydrogenated triamine is an intermediate for preparing the corresponding triisocyanate, which in-turn is useful in the preparation of polyurethane materials.

United States Patent Hoeschele 14 1 July 11, 1972 [54} 2,4-BIS(4-AMINOCYCLOHEXYL- 1 Relerences Cit d METHYL)CYCLOHEXYLAMINE UNITED STATES PATENTS [72] Inventor: Guenther Kurt Hoeschele, Wilmington, ,924 3/ 52 m -m 0/563 Del. 3,347,917 10/1967 Arthur ..260/563 2,683,730 6/1954 Seeger et al. ..260/453 1 Asslgnee= Pom de Nemwm and p y 3,153,088 10/1964 Arthur ..260/563 wflmingmn'Del' OTHER PUB ICATIONS L 1 22 Filed: Sept. 16, 1970 Zalikin et al., Soviet Inventions Illustrated, p. 9, 1966). [21] Appl.No.: 72,811

' Primary Examiner-Joseph Rebold Related U'S' Applicauon Data Assistant ExaminerDolph I-I. Torrence [62] Division of Ser. N0. 741,847, July 2, 1968, Pat. NO.

3,557,180. [57] ABSTRACT [52] U.S.Cl.... ....260/563 R, 260/5638 The triamine 2,4-bis(aminocyclohexylmethyl)cyclohe 51 1m.c1. ..C07c 87/42 Xylamine is p p y hydrogenation of (P- [58] Field of Search ..260/563 R, 563 B amimbenzynaniline- The hydmgenated "iamine is an intermediate for preparing the corresponding triisocyanate, which in-tum is useful in the preparation of polyurethane materials.

1 Claim, No Drawings 2,4-n1s 4- AMINOCYCLOHEXYLMETHYIJCYCLOHEXYLAMINE RELATED APPLICATIONS This application is a divisional of copending application Ser. No. 741,847, filed July 2, 1968 now U.S. Pat. No. 3,557,180.

BACKGROUND OF THE INVENTION Polyisocyanates are highly useful compounds which have gained wide acceptance as starting materials forthe manufac- 2,818,433, 2,974,168 and 3,163,666. Aniline and formaldehyde are reacted in the presence of a mineral acid. Hydrochloric acid is preferred, although other mineral acids, such as sulfuric acid, can be used. While the exact amount of acid to be used is not particularly critical, the practical range is between about 0.4 and 2 moles per equivalent of amine. The preferred range is about 0.8-1.0 moles per equivalent of amine. The mineral acid will, of course, form salts with the cyanate can be used. Examples of known aliphatic polyisocyanates are 1,6-hexamethylene diisocyanate, 4,4-

diisocyanate;

Though many of the known aliphatic isocyanates are more or less suitable for use in preparing such products as polyurethane coatings and foams, there is a need for an aliphatic isocyanate which has a functionality (isocyanato groups per molecule) greater than two. Isocyanates having a higher functionality generally yield faster curing coatings which are tougher and more stable against outdoor exposure and certain solvents than coatings prepared from lower-functional isocyanates. Foams prepared from higher functional isocyanates generally develop gel strength more rapidly and manifest improved compression set. Other highly desirable attributes of any isocyanate are low volatility (and thus low toxicity) and liquidity at normal operating temperatures for ease of storage and handling. Few, if any, of the known aliphatic isocyanates combine all these desirable attributes.

SUMMARY OF THE INVENTION This invention provides the new aliphatic triamine, 2,4- bis(4-aminocyclohexylmethyl)cyclohexylamine, and the corresponding triisocyanate, 2,4-bis(4isocyanatocyclohexylmethyl)cyclohexyl isocyanate. Novel polyurethane compositions prepared by reacting said triisocyanate with activehydrogen containing compounds are also provided.

DETAILED DESCRIPTION The triisocyanate of this invention correspond to the follow ing structural formula:

CON-@CHQNC o H@NCO hereinafter also called triamine." The triamine corresponds to the above-identified triisocyanate formula except the isoamines present and it is to be understood that the term mineral acid is meant to include salts of the acid with the amine. Also, the aniline which reacts with formaldehyde can be present as the free amine or as a salt of the mineral acid.

As is well known, the condensation of aniline and formaldehyde as described above produces a mixture of methylenebridged polyphenylene polyamines which include 4,4- methylenedianiline (MDA), 2,4-bis(4-aminobenzyl)aniline (the desired aromatic triamine starting material) and related higher polyamines. The relative proportions of these amines in the reaction product depends on the ratio of aniline to formaldehyde used. In order to maximize the yield of aromatic triamine, the aniline-formaldehyde ratio should be at least 2.021 and preferably about 2.8-3.0: l though higher and lower amine/formaldehyde ratios can be used.

5 After' the reaction is complete, unreacted aniline and methylenedianiline are removed by distillation, and the crude 2,4-bis(4-aminobenzyl)aniline further purified by distillation. The aromatic rings of the triamine are then hydrogenated by conventional procedures, illustrative of which is the method described in U.S. Pat. No. 2,606,925. Alternatively, the distillation residue remaining after removal of MDA can be hydrogenated directly without isolation of the aromatic triamine, and the eycloaliphatic triamine can then be isolated from the mixture of hydrogenated materials. The ring hydrogenation of the aromatic triamine proceeds smoothly to high yields of the aliphatic triamine substantially free of aromatic amines.

The eycloaliphatic triamine is a complicated mixture of various possible stereoisomers. The related diamine, 4,4- methylenebis(cyclohexylamine), exists in three stereoisomeric forms, and the presence in the compound of the third ar'ninocyclohexyl group increases the number of possible stereoisomers to eight. The ratio of the various stereoisometric forms will vary to a considerable extent with the exact conditions used in carrying out the hydrogenation. For discussion of the variation of stereoisomeric forms of the diamine see U.S. Pat. No. 2,494,563, column 1.

To obtain the corresponding triisocyanate, the triamine is phosgenated using conventional methods such as those described in U.S. Pat. Nos. 2,818,433, 2,974,168, 3,163,666

and 3,367,969. The conversion of the triamine to the triisocyanate does not affect the structural configuration and therefore the isomeric ratio of the triamine is substantially carried over to the isocyanate.

The triisocyanate and its mixtures with other aliphatic polyisocyanates, particularly 4,4'-methylenebis(cyclohexyl isocyanate) can be reacted with at least one active-hydrogen containing compound, i.e., polyols, polyamines and water, to prepare non-discoloring coatings, adhesives and flexible foams by methods well known in the art. In coating and adhesive fonnulations, the triisocyanate can be used to replace trifunctional aromatic isocyanate components. The inherently lower reactivity of aliphatic isocyanates can be compensated by the use of catalysts. In preparing non-discoloring flexible foams, the triisocyanate is preferably used in admixture with an aliphatic diisocyanate. While flexible foams can be prepared from such mixtures by a one-shot procedure, prepolymer and quasi-prepolymer procedures are preferred cyanato groups are replaced by amino groups. The triamine is because of the relatively low reactivity of aliphatic isoa viscous liquid boiling at about 198C. at 1 mm. Hg.

The starting material for the triamine is the corresponding aromatic triamine. The aromatic triamine is prepared by condensing aniline and formaldehyde by the procedure disclosed cyanates. Tetrarnethylguanidine is a preferred catalyst for the reaction of aliphatic isocyanates with water.

The usual polyether and polyester diols and polyols can be employed in preparing coatings, adhesives and foams based on in the following representative references: U.S. Pat. Nos. the triisocyanate; however, polyesters are often preferred because of their greater resistance to oxidation which complements the non-discoloring characteristics of the aliphatic isocyanates. Representative polyols useful in this invention are given in U.S. Pat. No. 3,248,373 to Barringer. Detailed information on formulations and procedures for preparing representative urethane coatings, adhesives and flexible foams can be found in Chapters V1], X and XI of "Polyurethanes: Chemistry and Technology, Part 11, Saunders and Frisch, 1nterscience Publishers (1964).

The triamine is useful as an intermediate in the preparation of the triisocyanate. The triisocyanate is highly useful in the preparation of such materials as polyurethane coatings and foams as described above. It has the important advantage of being a liquid at room temperature and thus is conveniently handled and stored. The triisocyanate has extremely low volatility which is a significant factor with respect to safety to personnel handling the material. Because of the known structure of the triisocyanate, it provides a convenient means of controlling the average functionality of reactants to be used in polyurethane preparation. A further advantage of the triisocyanate is that it contains one isocyanato group which is less reactive than the other two (attached to the central carbocylic ring) which is important in certain applications where it is desired to leave some isocyanato groups available for further reaction, e.g., moisture-cured coatings.

The invention will be further illustrated by the following examples wherein parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 a. Preparation of 2,4-bis(p-aminobenzyl)aniline Aniline and formaldehyde are reacted in the presence of hydrochloric acid using molar ratios of aniline to formaldehyde of about 3:1 and aniline to HCl of about 0.92:1. The reaction is carried out first at 20-42C. and then continued at about 65C. for about 4 hours. The reaction mass is added to aqueous sodium hydroxide to neutralize the amine hydrochloride. The aqueous and organic phases are separated, and unreacted aniline is distilled off leaving a crude reaction mass containing about 85.7 percent 4,4'-methylenedianiline. 3,346 grams of this crude product are distilled at a pressure of 0.5 mm. Hg to remove most of the methylenedianiline, leaving a residue of 477 g. 467 grams of this residue are transferred to a smaller flask and distillation is continued. After discarding 37 g. of a forerun, a total of 335 g. of distillate is collected (pot temperature of 290340C. at 0.5 mm. Hg) and 92.5 grams of residue remain in the flask. The distillate is recrystallized twice from toluene, and the product is further purified by continuous extraction with n-hexane for 4 hours to remove any trace of methylenedianiline. The purified compound, 2,4- bis(p-aminobenzyl)arriline, melts at 133-135C.

Analyses for amino nitrogen show the following,

Calculated for Found IO SI SI 13.85 13.7,13.9. b. Preparation of 2,4-bis(aminocyclohexylmethyl)cyclohe xylamine The compound prepared in paragraph (a) above is hydrogenated as follows:

A mixture of 100 ml. of dioxane, 50 g. of anhydrous ammonia, 15 g. of catalyst comprising 5 percent ruthenium on finely divided alumina, and 100 g. of 2,4-bis(paminobenzyl)aniline is hydrogenated in a reactor pressured with hydrogen at 5,000 psig at 210C. for one hour, with agitation. The reactor is cooled and vented, and the product is rinsed from the reactor with dioxane. The dioxane solution is freed of catalyst be filtration and is distilled to yield 2,4-bis(4- cyclohexylmethyl)cyclohexylamine boiling at 198C./ 1 mm. Hg. The product is a clear, colorless syrup. The distilled triamine has an amine equivalent weight as determined by titration with standard acid solution, of 107.7 (calculated, 107.2) and is substantially free of aromatic material, as shown by ultraviolet analysis.

Analyses show the following: Calculated for C H N C, 74.7; H, 12.23; N, 13.06; mol.

weight, 321.5. Found: C, 73.7; H, 12.2; N, 12.8; mol. weight (cryoscopic in benzene) 331, 335.

c. Preparation of methyl )cyclohexyl isocyanate A solution of 30 g. of the triamine prepared as described in (b), dissolved in 310 g. of dry o-dichlorobenzene, is saturated with anhydrous hydrochloric acid at -l20C. with efficient agitation. Phosgene is added to the resulting slurry at 165C. for about 2 hours until a homogeneous reaction mixture is obtained. The charge is swept with nitrogen to remove phosgene, and the solvent is distilled off under reduced pressure (20 mm. Hg) and finally at C. and 0.5 mm. Hg. The crude phosgenation product (35.4 g.) is purified by continuous extraction with petroleum ether (boiling range 30-60 C.). About 1 g. of the crude material is insoluble in petroleum ether and discarded. The extracted product is freed of solvent by distillation yielding an almost colorless viscous liquid.

2,4-bis(4-isocyanatocyclohexyl- Analyses show the following:

Calc. for Found u sa a a Molecular Weight (Cryoscopic method in benzene) 399.5 399 407 C, 69.2 68.6 68.5 H, 8.33 8.4 8.3 N,% 10.52 10.5 10.4 NCO, (ASTM D-1638-60T) 31.55 30.95

The structure of the 2,4-bis(4-isocyanatocyclohexylmethyl)cyclohexy! isocyanate is confirmed by nuclear magnetic resonance and infrared spectroscopy.

EXAMPLE 2 Crude methylenedianiline, prepared as described in Example 1, is distilled at reduced pressure to remove methylenedianiline. The residue comprising 2,4-bis(paminobenzyl)aniline and minor amounts of higher polyamines is hydrogenated by the procedure described in Example 1. The aliphatic triamine is isolated from the reduction mass by fractional distillation at 1 mm. Hg in a spinning band column. About 70 parts of triamine, substantially identical to that prepared in Example 1, is obtained for each 100 parts of starting residue. The distilled triamine is phosgenated according to the procedure of Example 1. The product, after extraction with petroleum ether, is obtained with about 90 percent yield based on the aliphatic triamine as a slightly yellowish clear liquid having an isocyanate content of 30.65 percent. A purer and completely colorless product is obtained by distillation in a falling film molecular distillation apparatus (6 inches of heated column, mean free path 2 mm.) at a pressure of 1 micron at a column temperature of -130C.

Analyses show the following:

The distillation apparatus used is described in Review of Scientific Instruments," Vol.31, No. 9, pgs. 1002-1004, 1960).

EXAMPLE 3 A prepolymer is prepared by mixing 80 parts of a polyester triol having an equivalent weight of about 1,000 (obtained by esterification of adipic acid with a mixture of diethylene glycol and trimethylolpropane) with 58 parts of a liquid mixture of stereoisomers of 4,4-methylenebis(cyclohexyl isocyanate) containing about 20 percent trans-trans isomer, -ypercent cistrans isomer and percent cis-cis isomer at room temperature and heating the resulting mixture for hours at 67C. The resulting prepolymer has an isocyanato group assay of 10.6 percent.

Foam A-A non-discoloring flexible foam is prepared from this prepolymer by a batchwise quasi-prepolymer procedure employing the following fonnulation.

Prepolymer 130.0 parts Triisocyanate of Example 11 22.0 parts Polyester triol described in this example 23.6 parts N,N-Dimethylformamide 9.5 parts Methylene chloride 8.0 parts Silicone surfactant for flexible polyester foams sold by Union Carbide as L-532. Described in Is-532, Silicone Surfactant for Polyester Urethane Formation," Product Information Bulletin, Union Carbide, 1966. 1.5 parts Water 3.72 parts Tetramethylguanidine 4.0 parts The materials are added in the order shown at room temperature and the resulting mixture is agitated for about 12 seconds with a high-speed mixer and then poured into an open container and allowed to foam. The formulation requires about 150 seconds to reach maximum height. The foam does not exhibit any shrinkage and has uniform fine cells. It has a density of about 2.0 lbs/cu. ft. After aging for 20 hours at 120C., the foam has a compression set of 27 percent by ASTM Method B (50 percent compression, 22 hours/70C./ 30 minute recovery).

Foam B-A second foam is prepared by the same procedure with the exception that the 22.0 parts of triisocyanate is replaced with a chemically equivalent amount (34.3 parts by weight) of a 77 percent by weight solution of the trimer of 4,4'-methylenebis(cyclohexyl isocyanate dissolved in 4,4- methylenebis(cyclohexyl isocyanate). The isocyanate assay of the trimer solution is 19.7 percent. The trimer solution is prepared by heating 100 parts of the liquid 4,4-

methylenebis(cyclohexyl isocyanate) previously described in this example in the presence of 2 parts of 1,l,2,4,4,5,5-heptamethylisobiguanide at 60-70C. until the isocyanate assay drops to the desired value and preventing further trimerization by the addition of 1 part of benzoyl chloride. Foam B reaches maximum height in about 120 seconds and does not exhibit any shrinkage. lts cell structure is somewhat coarser than that of Foam A. After aging for 20 hours at 120C. the compression set of Foam B is 59, over twice the value found for Foam A by the same test method.

Foam C-A third foam is prepared by substantially the same procedure used for Foam A with the exception that the 22.0 parts of triisocyanate is replaced with a chemically equivalent amount (21.8 parts by weight) of the liquid 4,4- methylenebis(cyclohexyl isocyanate) previously described in this example. Foam C rises to maximum height in about 130 seconds, does not shrink and has uniform fine cells. After 20 hours aging at 120C. its compression set is about 60, again over twice that found for Foam A by the same test method.

EXAMPLE 4 a. The triisocyanate product of Example 1 is mixed with an equal weight of the liquid 4,4'-methylenebis(cyclohexyl isocyanate) described in Example 3. The resulting mixture, which has an isocyanate content of 31.3 percent, is used to prepare a coating composition as follows;

54 parts of the mixture is mixed with parts of a hydroxyterminated polyester diol having an equivalent weight of 265 and a hydroxyl No. of about 205 (the diol is the reaction product of adipic acidand a mixture of ethylene glycol and propylene glycol containing 70 mole percent ethylene glycol) TABLE Hardness (determined by Sward Rocker) Cure Sward reading 1 day 4 5 days 24 10 days 28 For a discussion of the Sward Hardness Rocker seeOfficial Digest, Federation of Paint and Varnish Production Clubs, 26, 1030-8 (Nov. 1954). The apparatus is available from the Gardner Laboratory, 1nc., Bethesda, Md.

Abrasion Resistance (determined by means of a Taber Abraser, CS-l7 wheel, 1000 g. wt.)

Weight loss per 1000 Cure revolutions, mg. 1 week 1 15 1 month 86 Stress Strain Properties (measured by ASTM Method D 412-62T) Tensile strength Elongation at Cureat Break, psi Break, 1 week 3500 120 1 month 5150 b. When the above experiment is repeated using as the isocyanate component 53 parts of the liquid 4,4- methylenebis(cyc1ohexyl isocyanate) described in Example 3, the solution has a workable pot life of 4 days. Cast films take about 7-8 days to dry to a tack-free state as.opposed to less than 1 day for the films of part (a). The films are so soft that they have a Sward hardness of only 4 after 10 days and are not suitable for the determination of stress-strain data.

c. When films are prepared as in part (a) except using the triisocyanate as the only isocyanate component and the same stoichiometric proportion of the polyester, the solution has a somewhat shorter pot life. The films prepared are harder and more resistant to weather exposure than those of part (a).

What is claimed is:

l. 2,4-Bis(4-aminocyclohexylmethyl)cyclohexylamine. 

